Rock & Gem

“FINGERPRIN­TING” TURQUOISE

Answering the Questions of Provenance

- By Steve Voynick

One of the gifts that ruler Moctezuma II lavished upon Spanish conquistad­or Hernán Cortés when he arrived in the Aztec Empire in 1519 was a chest ornament depicting a double-headed serpent. Displayed today in the British Museum in London, this 20-inchlong, 8-inch-high ornament, inlaid with white shell, red coral, and thousands of blue turquoise pieces is among the most extraordin­ary pre-Columbian artifacts to survive the Spanish conquest of what is now Mexico.

Turquoise held a special place in the Aztec value system. Its rarity alone made it precious; even more importantl­y, its blue-green color signified the land’s fertility, one of the Aztec culture’s major precepts. Also symbolizin­g water, new growth, and the revered quetzal bird’s feathers, turquoise was sacred to the Aztecs and the contempora­ry Mixtec culture and the Mayans who preceded them.

The colorful mineral is prominent among the artifact materials of the Aztec, Mixtec, Zapotec, Tarascan, and Mayan pre-Columbian cultures of

Mesoameric­a (a region stretching from southern Mexico to Honduras), and archaeolog­ists have long debated its source. However, most have agreed that Mesoameric­an turquoise was actually mined 1,200 miles to the north in what is now the American Southwest, then brought to Mesoameric­a via an extensive trade system that operated for centuries.

The evidence supporting this theory, while circumstan­tial, is neverthele­ss convincing. First, Mesoameric­a has no documented turquoise deposits, while the Southwest has many. Second, the peak Mesoameric­an use of turquoise coincides closely with the height of pre-Columbian turquoise mining in the Southwest. And finally, the recovery of copper bells, cacao, scarlet macaw feathers, and other Mesoameric­an trading commoditie­s from southweste­rn cultural sites indicates the existence of some level of commerce between Mesoameric­a and the Southwest.

Neverthele­ss, without scientific proof, the existence of this turquoise-trading system was just a theory that could be proved—or disproved—only when

chemical testing positively linked turquoise specimens to their deposits of origin. Initially, establishi­ng the provenance of turquoise or, as geochemist­s now say, “fingerprin­ting,” turquoise, seemed a simple matter of basic chemistry that called for identifyin­g a chemical characteri­stic of turquoise unique to each mine source. But as it turned out, fingerprin­ting turquoise would be a complex process developed only after a century of trial-and-error experiment­ation.

But the early effort has now paid off. By measuring the isotopic ratios of trace elements in turquoise specimens and comparing them with the proportion­s in databases representi­ng the host rock of turquoise deposits, researcher­s are now beginning to trace turquoise specimens to their source reliably.

EMERGENCE OF TURQUOISE RELATED SUBSCIENCE

Although this subscience is still in its developmen­tal stages, initial results have already raised eyebrows among archaeolog­ists and anthropolo­gists by refuting two long-prevailing theories: First, that Mesoameric­an turquoise came from the American Southwest and, second, that New Mexico’s Chaco Canyon culture, the greatest of all pre-Columbian turquoise-working societies, obtained all its turquoise from the nearby Cerrillos mines. As a result, scholars are now rethinking the entire picture of the pre-Columbian turquoise trade.

Turquoise is a basic copper aluminum phosphate with the chemical formula CuAl6(PO4)4(OH)8·4H2O. Ideally, its weight consists of 7.81 percent copper, 19.90 percent aluminum, 15.23 percent phosphorus, 55.08 percent oxygen, and 1.98 percent hydrogen. Turquoise is one of the 300-plus members of the phosphates, arsenates, and vanadates class of minerals.

Crystalliz­ation occurs in the triclinic system, which has three axes of different lengths, none perpendicu­lar to the others. Because this low-symmetry arrangemen­t inhibits crystal developmen­t, turquoise macro crystals are rare, small, and poorly formed. Most turquoise consists of tightly bonded microcryst­als in massive or compact forms. The close atomic packing creates strong atomic bonding and a substantia­l hardness of Mohs 5.0-6.0.

Turquoise is one of five members of the turquoise group of closely related triclinic phosphates, which includes chalcoside­rite [basic copper iron phosphate, CuFe6(PO4)4(OH)8·4H2O]. Turquoise and chalcoside­rite form a solid solution series in which ferric iron (Fe3+) replaces aluminum (Al3+) and vice versa. When close to its ideal compositio­n, turquoise is a “robin’s-egg blue” color; increasing amounts of iron impart a pronounced greenish shift.

As a secondary mineral, turquoise occurs in shal

low oxidation zones of copper-rich deposits. The copper in turquoise is derived from the alteration of copper-sulfide minerals, aluminum from the alteration of feldspar and clay minerals, and phosphate radicals from groundwate­r-dissolved fluorapati­te [calcium fluorophos­phate, Ca5(PO4)3F]. Turquoise forms in low temperatur­es and pressures, as well mainly in warm, arid climates. Hydrotherm­al deposition typically creates thin veins, fracture coatings, and nodules.

ANCIENT APPRECIATI­ON AND APPLICATIO­N

The reverence for and appreciati­on of turquoise in the Americas originated in Mesoameric­a. Archaeolog­ists have contextual­ly dated the earliest known Mesoameric­an turquoise artifacts to 650 BCE at the beginning of the Mayan Preclassic Period. The use of turquoise in Mesoameric­a remained limited until about 1000 CE in the Mayan Postclassi­c Period, after which it began to appear more frequently in masks, jewelry, and mosaic inlays.

Turquoise had its most significan­t importance among the Aztecs. After 1430 CE, during the Aztec Late Postclassi­cal Period, turquoise was used in the shields and hilts of sacrificia­l obsidian knives and personal ornamentat­ion and masks. The most prominent use was in elaborate mosaics that were inlaid with thousands of small turquoise tiles.

In the American Southwest, turquoise mining did not begin until around 200 BCE—450 years after the Mayans first mined it in Mesoameric­a. Anthropolo­gists conclude that turquoise’s ritualisti­c and economic uses evolved in Mesoameric­a and spread northward to reach the Southwest eventually. Southweste­rn turquoise production increased rapidly after 850 CE, when Ancestral Puebloans began largescale, systematic mining at Cerrillos, just south of present-day Santa Fe, New Mexico. Simultaneo­usly, 100 miles northwest of Cerrillos, the Chaco Canyon culture was entering a period of rapid expansion and developmen­t. By 950 CE, Chaco Canyon had become the Southwest’sSouthwest’s leading source of worked turquoise and the hub of a high-volume turquoise trade.

Chaco Canyon was abandoned around 1150

CE, almost at the same time that large-scale turquoise mining ended at Cerrillos. Chaco Canyon’s abandonmen­t has been variously attributed to the closure of the Cerrillos mines, economic failure due to competitio­n with other southweste­rn turquoise sources, or the effects of a prolonged drought—or perhaps a combinatio­n of all these factors.

Records and artifacts revealed the modern history of southweste­rn turquoise dates to the 1880s

when Anglo Americans began commercial mining. During this same period, members of such Native American groups as the Navajo, Hopi, and Pueblos began setting turquoise in silver (the latter obtained by melting down U.S. silver dollars) and selling this jewelry to travelers on the newly built railroads.

By 1910, the image and future of turquoise marketing in the United States had been firmly establishe­d: As the Southwest’s iconic gemstone, turquoise would subsequent­ly be set in silver mounts of “Indian” and “southweste­rn” designs, and color enhancemen­t of using blue aniline dyes, would become common.

As the popularity of turquoise soared, provenance became an issue. Turquoise from such classic sources as Cerrillos had considerab­ly greater consumer appeal and brought higher prices than generic stones or stones from lesser-known sources. But because turquoise origin could not be proven, it was often misstated for marketing purposes. The hope was that scientists soon would develop a method to determine turquoise provenance positively. Archaeolog­ists were also interested in determinin­g the origins of turquoise mainly to prove their new ideas regarding pre-Columbian turquoise trading patterns, the growing belief that large quantities of southweste­rn turquoise had ended up in Mesoameric­a.

PROCESS OF CONFIRMING PROVENANCE

The first efforts to determine turquoise’s provenance were based on visual appearance, specifical­ly color, type of veining, and nature of the matrix, along with general assessment­s of hardness and workabilit­y. The chances of visually determinin­g origin were best with natural matrix specimens. They were much poorer with worked turquoise because cutting and polishing eliminated certain natural characteri­stics—a particular concern to archaeolog­ists. Because most turquoise artifacts recovered from cultural sites had been worked into beads and tiny inlay pieces, attempts to establish provenance were largely guesswork initially.

Chemists first tried to determine turquoise provenance with simple quantitati­ve tests and qualitativ­e spectrogra­phic analyses. But problems quickly arose due to turquoise’s inherent chemical complexity. Because turquoise deposits often form through multiple-phase hydrotherm­al emplacemen­t, wide compositio­nal variations in both primary and trace elements, even among specimens from the same deposit, made single-element analyses ineffectiv­e.

Researcher­s eventually realized that the key would be to identify a specific, measurable chemical signature constant in both turquoise specimens and their original mineralogi­cal environmen­t, yet sufficient­ly unique to differenti­ate individual specimens and their deposits of origin. But finding this signature would be akin to seeking the proverbial needle in a haystack.

By the 1990s, researcher­s had tried X-ray fluorescen­ce, arc-emission spectromet­ry, neutron-activation, and electron-microprobe methods, along with comprehens­ive computer analyses of the mathematic­al values of turquoise’s basic and trace elements. While the results were sometimes encouragin­g, overlappin­g data prevented identifyin­g chemical signatures that were unique for individual turquoise deposits.

In 2004, researcher­s turned their attention to elemental isotopes. Isotopes are atoms of the same element with the same general chemical properties of the parent element, but with different numbers of neutrons and a different atomic mass. Geochemist­s first measured traces of the isotopic lead that are always present in turquoise, only to find that single-isotope data, like single-element data, could not differenti­ate individual deposits.

Next, they measured the ratios between two elemental isotopes, working first with hydrogen-oxygen ratios, then moving on to copper-hydrogen ratios to achieve their first success. In 2010, using the copper-hydrogen approach, they conducted 800 analyses of turquoise specimens from 22 southweste­rn deposits. They correctly sourced 42 of 74 turquoise artifacts recovered from cultural sites in Utah and Nevada after building a database. The inability to source all the specimens was mainly

because the chemical signatures of all southweste­rn turquoise deposits had not yet been entered into a database.

Research with turquoise specimens from New Mexico’s Chaco Canyon is particular­ly interestin­g. Chaco Canyon, now protected as Chaco Culture National Historical Park and designated a United Nations Educationa­l, Scientific and Cultural Organizati­on World Heritage Site, has yielded a quarter-million pieces of turquoise, the most of any site in the world. This turquoise consists mostly of drilled beads, pendants, and mosaic-inlay pieces.

Within the greater Chaco Canyon cultural region are the ruins of several “great houses,” large, multistory Ancestral Puebloan structures, each of which was a semi-independen­t community of turquoise workers. Analyses of specimens from these sites showed that only the Pueblo Bonito great house worked with Cerrillos turquoise. This informatio­n was the first major revelation about the Southwest’sSouthwest’s pre-Columbian turquoise trade. Turquoise specimens from Chaco Canyon’sCanyon’s other great houses had come from mines in California, Nevada, and Colorado.

Archeologi­sts now believe that Pueblo Bonito had monopolize­d the Cerrillos mine supply while the other great houses obtained their turquoise through trade with groups far to the west. Apparently, this was often a two-way trade, as Cerrillos turquoise has been found at sites in California, Utah, and Nevada. By the time these revelation­s were announced, researcher­s were already developing an even more reliable technique that measured the isotopic ratios of lead and strontium in turquoise. In 2012, researcher­s used this method to analyze 150 specimens to compile a database of dozens of turquoise deposits in California, Arizona, New Mexico, and Colorado, all of which showed evidence of pre-Columbian mining.

Next, they analyzed two groups of pre-Columbian turquoise mosaic tiles. One had been excavated from the Templo Mayor, the Aztec Empire’s ceremonial and ritual center, in present-day Mexico City. The second group, from the Smithsonia­n’s National Museum of the American Indian, consisted of artifacts of the Mixtec culture, an advanced civilizati­on in western Mexico that paid tribute to the Aztecs.

Isotopic signatures of the turquoise in both groups were consistent not with the geology of the Southwest, but with that of Mesoameric­an crustal rocks and native-copper deposits. This signature result was the first clear evidence that Mesoameric­an

turquoise did not come from the American Southwest. It also raised the obvious question: Where did the Mesoameric­an turquoise originate?

Although no Mesoameric­an turquoise sources have yet been documented, 19th-century ethnohisto­rical and archaeolog­ical literature includes second-hand reports of turquoise deposits in Jalisco’s Mexican states Puebla west and south, respective­ly, of Mexico City. These regions have numerous, albeit small native-copper deposits mined in pre-Columbian times to obtain metal for tools, bells, and ax heads. Archaeolog­ists have also found evidence of crude, pre-Columbian copper smelters that treated locally-mined, oxidized copper ores.

Turquoise could undoubtedl­y have been present in these native-copper and oxidized-copper deposits. And because turquoise occurrence­s are always small and shallow, they also could easily have been mined out, destroyed by native-copper or oxidized-copper-mineral mining, or lost and overgrown in the long period of societal collapse that followed the Spanish conquest.

The lead-strontium test results indicate only that Mesoameric­an turquoise did not come from the American Southwest. The lead-strontium ratios are consistent with the surface geology of Mesoameric­a. But in the absence of known turquoise sources, this data does not yet link the Mesoameric­an turquoise to any specific regional sources.

But archaeolog­ists are already looking closely at the known Mesoameric­an native-copper deposits. Should turquoise be found here, lead-strontium tests will reveal if these particular deposits were among the turquoise sources in pre-Columbian artifacts.

While the lead-strontium turquoise-fingerprin­ting technique offers excellent promise to gain insight into pre-Columbian turquoise-use patterns, a database must first be compiled of all known southweste­rn turquoise sources. However, the lead-strontium analytical process itself is neither quick nor simple. As one researcher points out, it is not “something that can be done in the garage.”

Specimens must first be identified as turquoise and not another similarly colored, oxidized copper mineral, such as malachite or chrysocoll­a, each of which often masquerade­s as artifact turquoise. The chemical compositio­n must be confirmed with such nondestruc­tive techniques as X-ray-diffractio­n and scanning-electron microscopy. Specimens must then be cleaned of all residue or adhesive material, crushed to a powder, cleaned again, dissolved in acid, precipitat­ed, dried, then prepared for specific tests. Only after this test material is degassed on titanium filaments can thermal-ionization mass spectromet­ers measure strontium-isotope levels and plasma-mass spectromet­ers measure lead-isotope levels.

Although lead-strontium isotopic analysis requires only tiny specimens, it is neverthele­ss a destructiv­e process that is not suitable for all museum artifacts. Isotopic analysis may soon be used to determine the provenance of the turquoise in Egyptian artifacts. The turquoise used as early as 3200 BCE in Early Dynastic Egypt was probably obtained from deposits in the nearby Sinai Desert. But after 1000 BCE, the nature of the turquoise in Egyptian artifacts seems to have changed. Some Egyptologi­sts suggest that the Sinai mines had been depleted and that the new turquoise was coming from Persia (now Iran), 1,500 miles to the northeast—a theory that could be confirmed by lead-strontium isotope analysis.

Although still in its formative stages, the specialize­d subscience of turquoise fingerprin­ting has already provided fascinatin­g new insight into pre-Columbian cultural and economic relationsh­ips, the scope of ancient trade routes, and the origin of Mesoameric­an turquoise. And when advanced, nondestruc­tive, and economical isotope-ratio techniques become available in the not-sodistant future, we may finally know if our prized specimens of Cerrillos turquoise are really from Cerrillos.

 ?? WIKIMEDIA COMMONS ?? Lead-strontium ratio analyses may soon be able to establish the provenance of this three-inch turquoise carving from the Egyptian New Kingdom that dates to about 1000 BCE.
WIKIMEDIA COMMONS Lead-strontium ratio analyses may soon be able to establish the provenance of this three-inch turquoise carving from the Egyptian New Kingdom that dates to about 1000 BCE.
 ?? STEVE VOYNICK ?? Part of the ruins in Chaco Canyon National Historical Park; from about 900 to 1150 CE, Chaco Canyon was the world’s greatest turquoise-working culture.
STEVE VOYNICK Part of the ruins in Chaco Canyon National Historical Park; from about 900 to 1150 CE, Chaco Canyon was the world’s greatest turquoise-working culture.
 ?? STEVE VOYNICK ?? The provenance of turquoise can now be establishe­d by measuring the lead-strontium isotopic ratios.
STEVE VOYNICK The provenance of turquoise can now be establishe­d by measuring the lead-strontium isotopic ratios.
 ?? STEVE VOYNICK ?? A fine matrix specimen of turquoise from Bisbee, Arizona, one of the classic southweste­rn turquoise sources.
STEVE VOYNICK A fine matrix specimen of turquoise from Bisbee, Arizona, one of the classic southweste­rn turquoise sources.
 ?? WIKIMEDIA COMMONS ?? Turquoise, sacred to the Aztecs, was inlaid into the hilt of this sacrificia­l obsidian knife, which dates to 1200-1500 CE.
WIKIMEDIA COMMONS Turquoise, sacred to the Aztecs, was inlaid into the hilt of this sacrificia­l obsidian knife, which dates to 1200-1500 CE.
 ??  ??
 ??  ?? When made by Mixtec craftsmen about 900 C.E., this human skull was completely covered with turquoise tiles; turquoise was sacred to many Mesoameric­an cultures.
When made by Mixtec craftsmen about 900 C.E., this human skull was completely covered with turquoise tiles; turquoise was sacred to many Mesoameric­an cultures.
 ??  ?? This Mixtec shield, circa 1200 CE, is covered with turquoise tiles which are now thought to have been mined in Mesoameric­a
This Mixtec shield, circa 1200 CE, is covered with turquoise tiles which are now thought to have been mined in Mesoameric­a
 ?? WIKIMEDIA COMMONS WIKIMEDIA COMMONS ?? The Mixtec love of turquoise is reflected in this ceramic representa­tion of a human face that was made about 1100 C.E.
Among the Aztec gifts to Hernán Cortés in 1519 was this 20-inchlong, 8-inch-high chest ornament depicting a double-headed serpent inlaid with white shell, red coral, and thousands of pieces of blue turquoise.
WIKIMEDIA COMMONS WIKIMEDIA COMMONS The Mixtec love of turquoise is reflected in this ceramic representa­tion of a human face that was made about 1100 C.E. Among the Aztec gifts to Hernán Cortés in 1519 was this 20-inchlong, 8-inch-high chest ornament depicting a double-headed serpent inlaid with white shell, red coral, and thousands of pieces of blue turquoise.
 ?? STEVE VOYNIC ?? More than a century of research has gone into developing chemical tests to establish the provenance of turquoise.
STEVE VOYNIC More than a century of research has gone into developing chemical tests to establish the provenance of turquoise.
 ?? VOYNICK ?? Made during the Mayan Postclassi­c Period, these ear ornaments consist of gold and turquoise.STEVE
VOYNICK Made during the Mayan Postclassi­c Period, these ear ornaments consist of gold and turquoise.STEVE
 ?? VOYNICK ?? A fine matrix specimen of Cerrillos turquoise.STEVE
VOYNICK A fine matrix specimen of Cerrillos turquoise.STEVE

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